Preparation of organic compounds



Patented Niar. 17, 1942 PREPARATION or onoamc COMPOUNDS Herbert H.Guest, West Hartford, Conn.,' assignor to The J. B. Williams Company,Glastonbury, Conn, a corporation of Connecticut T No Drawing.

Application November-'9, 1937, Serial No. 173,608

21 Claims; (01. zen-404$ This invention relates to the production of organic compounds and particularly to the producemulsifying or wettingagents.

It is an object of this invention to provide, a new product suitable foruse as a detergent or in a soapless shampoo or to replace part or all ofthe soap in a dentifrice or detergent. Another object is to provide animproved procedure for producing such a product. Other objects willbecome apparent.

In carrying out the present invention, a hydroxyalkyl amine containingat least one hydrogen atom connected directly to the nitrogen of theamine group may be heated with an ester of a halogenated acid of thefatty acid series,

preferably in the presence of a high boiling solvent for the amine andthe ester.

As a specific example of the process, 50 parts by weight of methyl alphabromo myristate, carefully'purified, colorless and free from dibromotion of compounds useful as detergents or as ester, may be heated withparts of diethanolamine and 50 parts of diethylene glycol. The mixtureis heated at a temperature of about 180 to 200 C. for about to minuteswith stirring and refluxing of the solvent. The solvent and alcoholformed by the reaction are then removed by distillation, preferably atreduced pressure. The ester of the halogenated acid is believed to reactwith the diethanolamine in accordance with the following formula, wherelj-t represents the remainder of the fatty acid radical of thehalogenated acid: T

RCHBrCOOCH: 3[NH(CH1CH2OH)Z] RCHN(CH2CH1OII)2 come-memoir): (nocmommlumromon As indicated by this formula, hydrogen bromide from the estercombines with the diethanolamine to form a hydrobromide ofdiethanolamine and an amino-acid amide.

dethanolamine is very soluble in the reaction mixture. compound byaddition of sodium or potassium hydroxide which precipitates the halideas the alkali salt and frees the diethanolamine for further use. Thus aquantity of potassium hydroxide (8% parts'by weight), dissolved in alarge excess of ethyl alcohol parts by weight) may be added to thereaction mixture described above.

The potassium bromide which separates may be removed by filtration. Thealcohol may be distilled off and the residue can be used without furtherpurification.

The resulting amino-acid amide is suitable for The hydrobromide of Thehalide may be separated from this use as a substitute for soap insoapless shampoos, detergents and dentifrices. It is also useful as anemulsifying and wetting agent and as a binder for binding gasoline andalcohol.

Other saturated or unsaturated aliphatic hydrocarbon radicals containingfrom 6 to 22 and preferably about 8 to 18 carbon atoms, may be used inplace of the myristate. Hydrocarbon radicals containing 12 to 18 carbonatoms are particularly useful. Also, otherhalogens (such as chlorine oriodine) may be substituted for the bromine in the alphafhalogenatedester. The

methyl radical may also be replaced by other alkyl radicals. Examples ofother compounds useful for this purpose are methyl bromo laurate andethylchlorostearate. Many other suitable compohnds will be apparent fromthe examples given.

Other solvents may also be used, such solvents being preferably one thatcompletely dissolve the hydroxyalkyl amine and that at least partiallydissolve the halogenated ester of the aliphatic acid and which areofsufficiently high boiling point to avoid loss during the heating andrefluxing (preferably having a boiling point of C.

or more). Diethylene glycol or the ethyl or butyl ethers of diethyleneglycol or high boiling monohydric alcohols are examplesof suitablesolvents. Other hydroxyalkyl amines containing at least one hydrogenatom connected to the nitrogen of the amino group may be used in placeof the diethanolamine. For example, the monoethanolamine or aminescontaining other alkyl groups of the same or difierent types may be usedin place of the ethanolamine.

It is preferred to use an excess of the amine over the molecularreacting proportions as indicated in the example given. This excess maybe,

removed, along with the solvent, during the distillation under reducedpressure. This distillation may, for example, be carried out at atemperature of about 160 to 190 C. and at an absolute pressure of about5 to 20 millimeters of mercury. Operating. at C. and 10 millimeters ofpressure, for example, the distillation may be continued until theweight of distillate is approximately equal to the weight of solventandexcess amine.

The amount of solvent should be sufficient to form a homogeneoussolution on heating. An

excess does no harm in the reaction and may be removed during the vacuumdistillation, or otherwise.

The particular temperatures, proportions, times, etc. given in thisapplication are merely illustrative and are not intended to limit thescope of the invention. The terms used in describing the invention havebeen used in their descriptive sense and not as terms of limitationandit is intended that all equivalents thereof be included within the scopeof the appended claims.

No claim is made herein to particular uses of the products describedherein, which are claimed in applicant's copending application, SerialNo. 379,911, filed February 21, 1941.

I claim: I

1. A method for producing an organic compound comprising heating amember of the group consisting of monoand dialkylolamines, containing atleast one hydrogen atom connected to the nitrogen of the amino group,with an ester of an alpha halogenated aliphatic monocarboxylic acidcontaining 6 to 22 carbon atoms, in the presence of a high boilingsolvent for the amine and the ester, which solvent is substantiallyinert to the reactants under the conditions of operation.

2. A method for producing an organic compound comprising heating amember of the group consisting of monoand dialkylolamines, containing atleast one hydrogen atom connected to the nitrogen of the amino group,with an ester of an alpha halogenated aliphatic monocarboxylic acidcontaining 12 to 18 carbon atoms in the presence of and while refluxinga high boiling solvent for the amine and the ester.

3. A method for producing an organic compound comprising heating acompound of the group consisting of monoand diethanolamines with analkyl ester of an alpha halogenated fatty acid containing 8 to 18 carbonatoms, in the presence of a solvent for the amine and the ester having aboiling point of about 160 C. or more, which solvent is substantiallyinert to the reactants under the conditions of operation, to atemperature of about 170 to 210 C.

4. A method for producing an organic compound comprising heatingdiethanolamine, with an alkyl ester of an alpha halogenated fatty acidcontaining 12 to 18 carbon atoms, in the presence of diethylene glycolto a temperature of 180 to 200 C. while refluxing the solvent.

5. A method for producing an organic compound comprising heating amember of the group consisting of monoand dialkylolamines, containing atleast one hydrogen atom connected to the nitrogen of the amino group,with an ester of an alpha halogenated aliphatic monocarboxylic acidcontaining 6 to 22 carbon atoms in the aliphatic radical, and adding analkali hydroxide to the mixture.

6. A method for producing an organic compound comprising heating amember of the group consisting of monoand dialkylolamines, containing atleast one hydrogen atom connected to the nitrogen of the amino group,with an ester of an alpha halogenated aliphatic monocarboxylic acidcontaining 6 to 22 carbon atoms, in the presence of a high boilingsolvent for the amine and the ester, which solvent is substantiallyinert to the reactants under the conditions of operation, distilling offthe solvent and adding an alkali hydroxide to the mixture.

7. A method for producing an organic compound comprising heating amember of the group consisting of monoand dialkylolamines, containing atleast one hydrogen atom connected to the nitrogen of the amino group,with an ester of an alpha halogenated aliphatic monocarboxylic acidcontaining 6 to 22 carbon atoms, in the presence of a high boilingsolvent for the amine and the ester, which solvent is substantiallyinertto the reactants under the conditions of operation, distilling offthe solvent, adding an alkali hydroxide to the mixture, filtering toremove the alkali halide.

8. A method for producing an organic compound comprising heating acompound of the group consisting of monoand diethanolamines with analkyl ester of an alpha halogenated fatty acid, containing 8 to 18carbon atoms, in the presence of a mutual solvent having a boiling pointof about C. or over, which solvent is substantially inert to thereactants under the conditions of operation, to a temperature of aboutto 210 C. while refluxing the solvent, removing the solvent, adding analkali hydroxide in alcohol, filtering the mixture to remove alkalihalide, and removing the alcohol.

9. A method for producingan organic compound useful as a detergent,comprising heating a member-of the group consisting of monoanddialkylolamines, containing at least one hydrogen atom connected to thenitrogen of the amine, with an alkyl ester of an alpha bromo aliphaticmonocarboxylic acid containing 8 to 18 carbon atoms and adding an alkalihydroxide to the resulting mixture.

10. A method for preparing an organic compound suitable for use as adetergent, comprising adding diethanolamine and diethylene glycol tomethyl alpha bromo myristate and heating the mixture at'about 180 to 200C. for about 60 to 90 minutes while stirring and refluxing the solvent,removing the solvent and adding potassium hydroxide dissolved in ethylalcohol, filtering the mixture to remove potassium bromide, anddistilling to remove the alcohol.

11. A new product resulting from the heating of an ester of an alphahalogenated aliphatic monocarboxylic acid containing 6 to 22 carbonatoms in the aliphatic radical with a member of the groupconsisting ofmonoand dialkylolamines, containing at least one hydrogen atom connectedto'the nitrogen of the amino group, in the presence of a solvent for theester and the amine, which solvent is substantially inert to thereactants under the conditions of operation.

12. A new product resulting from the heating of an ester of an alphahalogenated aliphatic monocarboxylic acid containing 12 to 20 carbonatoms with an ethanolamine having at least one hydrogen atom connectedto the nitrogen of the amino group, in the presence of and whilerefluxing a mutual solvent for the ester and the amine, which solvent issubstantially inert to' the reactants under the conditions of operation,and

amines containing at least one hydrogen atom connected to the nitrogenof the amino group,

. and treating the resultant product with an alkali hydroxide.

14'. A new product resulting from the heating of an ester of an alphahalogenated aliphatic monocarboxylic aliphatic acid containing 6 to 22carbon atoms at about 170 to 210 C. with a member of the groupconsisting of monoand dialkylolamines containing at least one hydrogenatom connected to the nitrogen of the amino group, in the presence ofand while refluxing a high boiling solvent for the amine and the ester.which solvent is substantially inert to the reactants under theconditions or operation, removing the solvent, treating the product withpotassium hydroxide in an alcohol, and removing the potassium halide andalcohol. I

15. A new product resulting from heating methyl alpha bromo myristatewith diethanolamine and diethylene glycol at a temperature of about 180to 200 C. while agitating and-refluxing, distilling oi! the solventunder reduced pressure,

adding an alcohol solution of potassium hydroxide, filtering, anddistilling oi? the alcohol.

16-. A method for producing an organic compound comprising heating acompound 01 the class consisting of monoand dialkylolamines, containingat least one hydrogen atom connected to the nitrogen of the amino group,with an ester of an alpha halogenated aliphatic monocarboxylic' acidcontaining 6 to 22 carbon atoms in the aliphatic radical.

17. A method for producing an organic compound, comprising heating acompound of the class" consisting of monoand dialkylolamines, containingat least one hydrogen atom connected to the nitrogen of the amino group,with an ester 0! an alpha halogenated aliphatic monocarboxylic acidcontaining 6 to 22 carbon atoms in the allphatic radical in the presenceoi a solvent for the amine and the ester, which solvent is substantiallyinert'to the reactants under the-conditions of operation.

18. A new product resulting from the heating of an ester of an alphahalogenated aliphatic monocarboxylic acid containing 6 to 22 carbonatoms in the aliphatic radical with a compound of the class consistingof mono and dialkylolamines containing at least one hydrogen atomconnected to the nitrogen of the amino group.

. 19. As a new product of manufacture, analkylol amide of an alkylolamino aliphatic acid containing 6 to 22 carbon atoms in the aliphaticradical.

20. As a new product of manufacture, a dialkylol amide of a dialkylolamino aliphatic acid containing 6 to 22 carbon atoms in the aliphaticradical.

21. As a new product of manufacture. a diethanol amide of a diethanolamino aliphatic 7 acid containing 6 to 22 carbon atoms in the aliphaticradical. v

HERBERT H. GUEST.

